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Benefit and safety aspects of nanotechnology
-From the viewpoint of carbon nanotubes for a low-carbon society-
M. Endo
Shinshu University
Japan
OECD Conference on
Potential Environmental Benefits of
Nanotechnology:Fostering Safe Innovation-Led Growth
Conventional technology has contributed to building our fertile but
environmentally unfriendly civilization.
From now on, high-tech such as emerging nanotechnology will
contribute to realize the sustainable world.
And we have to start RIGHT NOW
Contents1. Nanotechnology and Carbon Nanotubes (CNT)
2. Manufacturing and green fuel production by CNT Process
3. CNT applications to lithium-ion battery (LIB) and LIB-based
electric vehicle for ultra low emission
4. Lead-acid battery using CNT and its contribution to the
Environment
5. CNT composite materials and its environmental effect
6. CNT composite rubber and oil development and water saving
7. The role of impurities to the safety issue of CNT
8.Conclusions; Green and safe innovation led by CNT for the
future of our planet
Layered Materials (1959)
What could we do with layered structures with just the right layers? What would the properties of materials be if we could really arrange the atoms the way we want them. They would be interesting to investigate theoretically. I cant see exactly what would happen, but I can hardly doubt that when we have some control of the arrangement of things on a small scale, we will get an enormously greater range of possible properties that substances can have, and of different things that we can do.
R. P. Feynman
There is Plenty of Room at the
Bottom
December 29, 1959
1. Nanotechnology and Carbon Nanotubes (CNT)
Diamond
Graphite
CNT
5nm
Single walled
carbon
nanotube
Carbon nanotube
Millionth of a millimeter thick carbon cylinder
DWCNT
Multi-walled Carbon nanotubes
2m
PAN-based Carbon Fiber
1nm
Carbon Nanotube
M.Endo
Space Elevator
The goals of the NNI are to:
Maintain a world-class research and development program aimed at realizing the full potential of nanotechnology;
Facilitate transfer of new technologies into products for economic growth, jobs, and other public benefit;
Develop educational resources, a skilled workforce, and the supporting infrastructure and tools to advance nanotechnology; and,
Support responsible development of nanotechnology
Now, CNT research is shifting from well-established basic science to
also application technology !
Source: http://www.nano.gov/html/about/home_about.html
Safety for success !
Catalytic CVD Method
Industrially applied for mass-production
Possibility and potentiality for controllability of
MW- ,DW- and SW-NT structure
2, Manufacturing and Green Fuel by CNT process
5nm
4.039nm0.377nm
3.208nm
Single, double and multi-walled
CNTs by CCVD process using
iron particle as catalyst
Fe catalytic particle
A. Oberlin, M. Endo,
and T. Koyama,
Journal of
Crystal Growth
32, 335-349 (1976)
A. Oberlin, M. Endo,
and T. Koyama,
Journal of
Crystal Growth
32, 335-349 (1976)
The first one is responsible
for the formation of the
inner core containing long,
straight and parallel carbon
lavers cylindrically rolled
around a hollow tube.
A. Oberlin, M. Endo,
and T. Koyama,
Journal of
Crystal Growth
32, 335-349 (1976)
Exposed SWNT during
the growth of crossing the
tubes
A. Oberlin, M. Endo,
and T. Koyama,
Journal of
Crystal Growth
32, 335-349 (1976)
Double layered carbon nanotube
in the core of the VGCF
A. Oberlin, M. Endo,
and T. Koyama,
Journal of
Crystal Growth
32, 335-349 (1976)
A. Oberlin, M. Endo,
and T. Koyama,
Journal of
Crystal Growth
32, 335-349 (1976)
A. Oberlin, M. Endo,
and T. Koyama,
Journal of
Crystal Growth
32, 335-349 (1976)
2 n m2 n m
CNT grown from an Iron catalyst particle
M. Endo
American Chemical
Society,
CHEMTECH,
September, 568-576,
(1988).
M. Endo,American Chemical Society, CHEMTECH, September, pp.568-576, (1988).
100 300 5000
20
40
60
80
100
Diameter of Fe particle ()
Rela
tive y
ield
(%
)
M. Endo American Chemical Society,
CHEMTECH, September, pp.568-576, (1988).Fluidization seeding permits better
control of the catalyst-feed ratio
and the product aspect ratio.
Fluidization- produced VGCF has a
crystallographic structure similar
to that of substrate-produced
VGCF, but with much smaller
hollow tubes of 2-3 nm (Figure 9).
The TEM image shows the catalyst
particle at the end of the growing
precursor fiber; it is not yet covered
with hard, graphite-like carbon
layers and can still actively assist
fiber growth in the longitudinal
direction. The resultant thin fibers
have a continuous, thin, hollow tube
as shown in Figure 11b.
M. Endo
American Chemical
Society,
CHEMTECH,
September, pp.568-
576, (1988).
Growth model of CNT by floating catalyst
MWCNT(VGCF) mass production
system and commercialization started
since 1988
hydrocarbon
(benzene) +
catalytic particles
gas outlet
H2
CNT
hydrogen
gas outlet
M.Endo, Japanese Pat.
, , Vol.24, No.5, pp.227-237, (1986).
M. Endo, American Chemical Society,
CHEMTEC, 568-576, (1988).
First stage of early 15 years, the productivity had increased by 1015 times
Mass produced CCVD multi -walled CNT (Dia. 40nm)
1
CNT manufacturing process itself is toward the hydrogen economy as a carbon
fixation and hydrogen production system, when it becomes enough large
Top cover
Safety vent
Gasket
PTC
Insulator
Anode can
Insulator
Cathode Anode
Separator
Anode lead (Cu)
Cathode lead (Al)
Structure of LIB practical cellCommercialization started since 1991 by SONY
Ref :
Sonys catalog, Lithium ion rechargeable battery, ACG-4012-N-9707-P3-002, 1977.
M. Endo, T. Karaki, T. Fujino New ceramics 1988; 4: 46-52, (In Japanese)
M. Endo, T. Hayashi, Y. A. Kim, H. Muramatsu, Development and application of carbon nanotubes, Jap. J. Appl. Phys., 45, 4883-4892 (2006).
3. CNT applications to lithium-ion battery (LIB) and LIB-based Electric Vehicle
for ultra low emission
Toyotas plug-in car
model
Principle of operation of Li-ion-Battery
LiCoO2Graphite
Li
O
Co
Endo lab.
Graphite sheet LiC18 LiC6
5m
Cu foil
MWCNT
M. Endo, Y. A. Kim, T. Hayashi, K. Nishimura, T. Matsushita, K. Miyashita
and M. S. Dresselhaus, Carbon, Vol.39, pp1287-1297, (2001).
70
100
95
85
90
80
0 10 20 30 605040
Cyclic umber
Rel
ati
ve c
harg
e i
n d
isch
arg
e c
ap
aci
ty
%
0% 1% 10%5%VGCF
Artificial graphite (HTT2500)with VGCF
Cyclic characteristics of synthetic graphite anode
as a function of weight percent of CNF(MWCT)
M. Endo et al., Carbon, 39, 1287-1297 (2001).
Schematic model to absorb
the stress by NT for Li-ions
intercalation to graphite
host
7.15
6.625.83
4.51
2.39 Power/Heating
Industry
Deforestation
Transport
Household
Total
7.15
6.62
5.83
2.391.80
26.5 Billion Tons
IPCC Fourth Assessment Report, WGlll, 2007. World Business Council for Sustainable Development, 2004
EDMC / Directory of Energy and Economic Statistics 2007
Overview of Global CO2 Emissions
in 2004
[109 t]
Plug-in HV
[109 t]
10% Decrease)Reference
Ministry of Land, Infrastructure, Transport and Tourism, Japan
If cars all over the world become Plug-in Hybrid Vehicle...
23.8 Billion Tons
(-3Bt=
By M.Endo
Key tech,
LIB
(HEV, EV, FCEV Plug-in car)
MWCNT can contribute to the21st centurys
environment, energy and information technology by LIB !
Coming soon the age of full electric car
The Automotive Battery The Motorcycle Battery (Sealed type)
Cover (Polypropylene)
Container (Polypropylene)
Anode: lead grid filled with spongy
lead
Separator (Polyethylene)
Anode (Pb)
Cathode: lead grid filled with PbO2
Cover (PP or ABS)
Container(PP or ABS)
H2SO4 electrolyte
Separator (Glass fiber or Synthetic fiber)
H2SO4 electrolyte
cathode
anode
Pb+PbO2+2H2SO4 2PbSO4+2H2O
Construction of Lead-Acid Batteries~Since 1860, performance improvement was only 50% ~
4. Lead-acid Battery using CNT and its contribution
to the Environment
RoHS directive since 2003 led to the reduction of Pb consumption
except rechargeable lead acid battery for motor vehicles (Japan)
Lead consumption
Lead production
World market for production and consumption of Lead
Illegal disposal of the lead-acid battery will happen frequently by the rising
motorization in the world, and which should be protected for global environment.
10Tt/Y
Larger part of Pb consumption is for the
lead-acid batteries such as for cars and
electric bicycles.
Model of Electronic Conductive Network in Active
Material with CNT ( from Yuasa Journal)
Advanced
Lead-Acid
Battery
Annual usage of PbO in Japan is 300 thousand tons
0 200 400 600 800 1000
40
60
80
100
Change in the Cell Capacity During the
Charge-Discharge Cycling Test ( at 25)
(by S. Hojyo from Yuasa Journal)
Cycling charge and discharge regime
Discharge:0.67A to 1.70V/cell
Charge:7.35V (max1.5A) -6H
Cycles
Dis
cha
rge
cap
aci
ty (
%)
Addition of MWCNT to
negative plate
No CNT
aditive
Superior battery life
Built-in type
car battery,
Optical network unit
M. Endo et al., Vapor-grown carbon fibers (VGCFs) Basic properties and battery application,
Carbon, Vol.39, pp1287-1297, (2001).
ConverterInverter
Lead Acid Battery
Engine
Advanced Lead Acid Battery by Incorporating
MWCNT for Diesel Engine-based Hybrid Bus
0.1mm
0.2mm
Precise plastic composite based on nanotubes
High tribological properties
Superior transcribing properties injection molding
The gear(a) made by MWNT composite material
by injection molding
5.CNT Composite Materials and its Environmental Effect
CNT/ plastic composite is useful for
windmill of wind-power generation
composite
Collaboration; Nissin Industry and M.Endo
Much lighter weight and strong as steel !
Carbon Nanofiber composite material project NEDO&Ministry of Economy)
(3) Structures and properties of CNT/Al systems
CNT/Al/N/O interfacial
surface phaseAl matrix phase
Huge cells Baskets
Cage cellulation
Cellulation in Al/CNT composite
ightness
Ant
corrosionThermal
expansion
FC250Al AC2B
m
0
500
50
01000
0
0
10
0
600
150
0
CompositesCast-iron
m
0
500
50
01000
0
0
10
0
600
150
0
Properties of the composites
Strength(MPa)
Thermal
resistance
Thermal conductivity W/mKW/mK
Comparison of the strength
Mg/CNT (Si coated) composite as light as
engineering plastics
Si coated
CNT/Aluminum
306 kg
Aluminum
138 kg
Plastics
117 kg
Gum
66 kg
Glass
34 kg
Others
53 kg
CNT/Magnesium197 kg
Aluminum
138 kg
Plastics
117 kg
Gum66 kg
Glass
34 kg
Others
53 kgSteel
892 kg
Aluminum
138 kg
Plastics
117 kg
Gum
66 kg
Glass
34 kg
Others
53 kg
Material Ratio for Automobiles*1
CNT/Aluminum
CNT/Magnesium
CNT/Aluminum
CNT/MagnesiumTotal
1300 kg
Total
714 kg
Total
605 kg
45.1%
53.5%
Al and Mg/CNT composites can provide light weight and
high safety flamebody
*1 TOYOTA Technical Review,
Vol.53, 219(2004)
million tons
60 million tons
Decrease of CO2 Emission (Calculated with CO2 Emission - Weight Relation*1)
-60 million tons
-72 million tons
50.0%
60.0%
CNT/Aluminum
CNT/Magnesium
Steel
CNT/Aluminum
CNT/Magnesium
(*1 Ministry of Land, Infrastructure, Transport and Tourism Japan)
(*2 JAMA, Japan Automobile Manufacturers Association )
of CO2/year
of CO2/year
of CO2/year
120
of CO2/year
48 million tonsof CO2/yearcar
Run: 10,000 km/year
Production: 60 million cars/year*2
0.2% decrease
0.3% decrease
CNT Rubber Composite for Oil Development and Water Saving
O-ring(a)
Init
ial R
eser
vo
ir P
ress
ure
(M
Pa
)
Reservoir Temperature ()
0
Present Work
Mary AnnMarnock
Eugene Island
North Ossum
(117, 62MPa)
Mobile Bay
South Texas(222, 91MPa)
Walter O&G
Mobile Bay 862(215, 129MPa)
Current
Technology
(b)
Figure S1. (a) Downhaul devices in underground resources probing using rubber seals as a key
component and (b) the distribution of temperature and pressure of the current oil wells, for example.
Note that our developed innovative technique will allow us to excavate oil from unreachable deposits
found deeper and at higher temperatures (as high as 260 C at 239 MPa). The authors would like to
thank Dr. T. Baird for his permission to use his original figure in High-Pressure, high-temperature well
logging, perforating and testing, Schlumberger Oilfield Review, 50-67 (1998)
M.Endo et al., Advanced Functional Mater.,18,3403(2008)
(Source: British
Petroleum World
Energy Statistics)
(Source: Calculated based on Life Cycle
Inventory Analysis of Fossil Energies in
Japan /
The Institute of Energy Economics, Japan
(1999) Gross Heating Value Base
Comparison of Greenhouse Gas Discharge (CO2 equivalent )
from Fossil Fuel by LCA
Electric powewr generation from natural resources in various countries
Immersion time (hours)
0200 400 600 800 1000
50
100
150
200
Res
idu
al c
hlo
rine
con
centr
atio
n (
ppm
)
Comp-3
Current
0
250
Figure Variations of the chlorine concentrations of chlorine solutions containing the carbon black
(Current) - and multi-walled carbon nanotubes (Comp-3) -incorporated rubber composites as a function of
immersion time. The chlorine solution containing current sample become opaque whereas there is no
changes in the solution containing Comp-4 sample (see Insets).
(Valve; opening-closing)Endurance test
Comp-3; 300,000 times
Current; 50,000 times
Multi-walled Carbon Nanotube-filled Rubber Nanocomposites for
Environmentally Durable Valve Sealant to Prevent Water Leakage
The rubber composite
has five times longer
durability.
Present rubber
composite is very
useful for Water warks
to prevent the water
leak for 5 times longer
than current rubber.
World Wide 400 million t/year CO2 Redaction
Present rubber can contribute to the CO2 -1.5% reduction per year and save the
clean water in world wide scale
Safety for Success !Pathological reactions on CNT in mice andexpected bio/medical applications
M. Endo and S. Koyama (Shinshu University, Japan)Collaboration with NIOSH Dr. V.Castranova
Methods
Animals: Mice
Materials: CNT vs Asbestos
Implantation: Subcutaneous tissue
Period: 6 months
Histology: H-E stain
Active oxygen species ,scavenged by agent as iron, are considered to inactivate
enzymes in the cells, damage DNA and destroy lipid membrane which should
cause every disease, aging as well as cancer as far as the most recent medical
research is concerned. In this experiment, the iron content is controlled as low as
200 ppm or less.
abdominal cavity of mice
Subcutaneous
implantation
Aspiration
&
inhalation
Testicles
Causing mesothelioma , if inhaled, and if they migrate to the edge of the
lungs ?
7.The role of Impurities to the safety of CNT and mouse plumonary responce
x40
x400
SWCNT(HIPCU)
4 weeks after subcutaneous implantation
1.Thicker granulomatous tissue
2. Suggesting more active inflammatory
response of SWCNT than MWCNT
S. Koyama & M. Endo, Carbon 44, 1079-
1092, 2006
Are there differences of biological responses depending on the property of Carbon
nanotubes?
To be publishedS.Koyama, M.Endo et al; In vivo immunological toxicity in mice of carbon
nanotubes with impurity, Carbon 47 (2009)1365
Proinflammatory (TNF, IL-6) cytokines
1.5
6.5
11.5
16.5
21.5
26.5
31.5
36.5
41.5
46.5
0 day 2 weeks 4 weeks 8 weeks
pg
/ml
TNF
Control
MWCNT-low
Purification
MWCNT-high
Purification
1.5
6.5
11.5
16.5
21.5
26.5
31.5
36.5
41.5
46.5
51.5
0 day 2 weeks 4 weeks 8 weeks
pg/m
l
I L -6
Control
MWCNT-low Purification
MWCNT-high Purification
Tumor necrosis factor alpha (TNF, cachexin or cachectin) is an important cytokine involved in systemic inflammation and the acute phase response.
IL-6: secreted by macrophages, induces acute phase reaction. Interleukin-6 (IL-6) is a pro-
inflammatory cytokine secreted by T cells and macrophages to stimulate immune response to trauma, especially burns or other tissue damage leading to inflammation.
Th1 (IL-12, IFN) cytokines
IFN
1.5
201.5
401.5
601.5
801.5
1001.5
1201.5
1401.5
1601.5
0 day 2 weeks 4 weeks 8 weeks
pg
/ml
Control
MWCNT-low
Purification
MWCNT-high
Purification
IL-12
1.5
6.5
11.5
16.5
21.5
26.5
31.5
36.5
0 day 2 weeks 4 weeks 8 weeks
pg
/ml
Control
MWCNT-low
Purification
MWCNT-high
Purification
IL-12: NK cell stimulation, Th1 cells induction.
Interleukin 12
(IL-12) is an
interleukin
that is
naturally
produced by
macrophages
and human B-
lymphoblastoi
d cells (NC-
37)in response
to antigenic
stimulation.
Interferon-is secreted by T-cells and natural killer lymphocytes.
All classes of
interferon
production.
Th2 (IL-4, IL-10) cytokines
IL-10
1.5
21.5
41.5
61.5
81.5
101.5
121.5
141.5
0 day 2 weeks 4 weeks 8 weeks
pg
/ml
Control
MWCNT-low
Purification
MWCNT-high
Purification
IL-4
1.5
6.5
11.5
16.5
21.5
26.5
31.5
36.5
0 day 2 weeks 4 weeks 8 weeks
pg
/ml
Control
MWCNT-low
Purification
MWCNT-high
Purification
IL-4: involved in
proliferation of B cells, and the
development of T cells and mast cells. Important role in
allergic responses.
IL-4 is a cytokine
that stimulates the
proliferation of
activated B-cells, T-
cells, and
differentiation of
CD4+ T-cells into
Th2 cells, among
other effects. It is a
key regulator in
humoral and
adaptive immunity.
IL-10: inhibits Th1 cytokine production.
Interleukin-10 (IL-10), also known as human cytokine synthesis inhibitory factor
(CSIF), is an anti-inflammatory cytokine, capable of inhibiting synthesis of pro-
inflammatory cytokines like Interferon-gamma, IL-2, IL-3, TNF and GM-CSF by
cells such as macrophages and the Type 2 T helper cells.
Summary
Carbon nanotubes should be purified to make it
free of several kinds of contaminations that are
formed during production processes.
It should be also better to develop the increased
biocompatibility of carbon nanotubes.
Viability Studies of Pure Carbon- and
Nitrogen-Doped Nanotubes with
Entamoeba histolytica : From
Amoebicidal to Biocompatible
StructuresAna Laura Elas, Julio Csar Carrero-Snchez,Humberto Terrones, Morinobu Endo, JuanPedro Laclette, and Mauricio Terrones ;
Nanoletter
Viability Studies of Pure Carbon- and Nitrogen-Doped Nanotubes with Entamoeba
histolytica : From Amoebicidal to Biocompatible StructuresAna Laura Elas, Julio Csar Carrero-Snchez,Humberto Terrones, Morinobu Endo, JuanPedro Laclette, and Mauricio Terrones ; Nanoletter
The discussion of what makes nanotubes
safe or harmful has to be based on science,
and has to be handled carefully.
TGA curves of non-mixed and NaCl-mixed MWCNT-20 (a) and
MWCNT-80 (b) for various mixing ratios of MWCNTs:NaCl
Res
idual
quan
tity
(%
)
Temperature ()
200 400 600 8000
20
40
60
80
100
0w/w%
NaCl
0.5w/w%
NaCl0.1w/w%
NaCl1w/w%
NaCl
0w/w% NaCl
(as-grown)
(a) MWCNT-20 (HTT:2600) (b) MWCNT-80 (HTT: 2800)
Temperature ()
200 400 600 8000
0w/w%
NaCl0.5w/w%
NaCl
0.1w/w%
NaCl
1w/w%
NaCl
Res
idual
quan
tity
(%
)
0w/w% NaCl
(as-grown)20
40
60
80
100
M. Endo et al., Sodium Chloride-Catalyzed Oxidation of Multi-Walled Carbon
Nanotubes for Environmental Benefit; J. Phys. Chem. B 110(24), 12017 (2006).
Responsible production ;For environmental issue in the CNT mass production era
Functions and Applications of Carbon Nanotubes
EMI
Bio-Sensor
Bio/Medical
Electric Conductivity
Hybrid Vehicle
Sensing
IT
Advanced Composites
Energy
Strength
Secondary
Battery
CapacitorFuel Cell
Thermal Device
Display Device
Bio compatibility
Catalyst
Physiology
Absorption
Adsorption
Morphology Mechanics
Electronic Engineering
Thermology
Thermal Conduction
Field EmissionEnergy Exchanger
MEMS
Semiconductor
Heat Exchanger
Modulus
Electric Vehicle
HE Device
Chemical Engineering
FUNCTIONS
APPLICATIONS
Environment
X-ray/ion source
8.Conclusions; Green and Safe Innovation led by CNT for the Future of our Planet
Conclusions1. Nanotechnology as safe and innovative technology is changing
our way of life.
2. Nanotechnology will solve the currently faced environmental andenergy problems
3. The viability of carbon nanotubes strengthens with itscommercialization after a detailed clarification of theirenvironmental and health safety issue
4. We have proceeded beyond the first mountain of science, thesecond mountain of technology and the third mountain ofeconomy by successful large-scale production of carbonnanotubes at a reasonable cost with the concept of responsibleproduction and uses.
5. Now we are striving to climb the mountain of society. By sharingthe all information on risks and benefits of the materials with allstakeholders, we will finally reach the top of a nanotubemountain and prove the carbon nanotubes to be the safeinnovative materials in the 21st century.
Society
Science
Technology
Economy
Carbon nanotube, as a leading-edge
of nanotech, must go beyond the four
mountains for realization of safe and green
innovation in the 21st century.
Worldwide collaboration on science and
technology including safety issue is the
key for big success by getting social
agreement.